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as those displayed in Table 14.2. The table lists initial rate data for four experiments in which the reaction

was run at pH 7.0 and 25C but with different initial concentrations of cisplatin. Because the reaction rate

increases with increasing cisplatin concentration, we know this cannot be a zeroth-order reaction.

Comparing Experiments 1 and 2 in Table 14.2 shows that the reaction rate doubles [(1.8 105 M/min)

(9.0 106 M/min) = 2.0] when the concentration of cisplatin is doubled (from 0.0060 M to 0.012 M).

Similarly, comparing Experiments 1 and 4 shows that the reaction rate increases by a factor of 5

[(4.5 105 M/min) (9.0 106 M/min) = 5.0] when the concentration of cisplatin is increased by a factor

of 5 (from 0.0060 M to 0.030 M). Because the reaction rate is directly proportional to the concentration of

the reactant, the exponent of the cisplatin concentration in the rate law must be 1, so the rate law is rate

= k[cisplatin]1. Thus the reaction is first order. Knowing this, we can calculate the rate constant using the

differential rate law for a first-order reaction and the data in any row of Table 14.2. For example,

substituting the values for Experiment 3 into Equation 14.19,

Table 14.2 Rates of Hydrolysis of Cisplatin as a Function of Concentration at pH 7.0 and 25C

nt M) (M/min)

Experime [Cisplatin]0( Initial Rate

nt M) (M/min)

Knowing the rate constant for the hydrolysis of cisplatin and the rate constants for subsequent reactions

that produce species that are highly toxic enables hospital pharmacists to provide patients with solutions

that contain only the desired form of the drug.

Example 4

At high temperatures, ethyl chloride produces HCl and ethylene by the following reaction:

CH3CH2Cl(g)HCl(g)+C2H4(g)CH3CH2Cl(g)HCl(g)+C2H4(g)

Using the rate data for the reaction at 650C presented in the following table, calculate the reaction order with respect

and determine the rate constant for the reaction.

Initial

Experime [CH3CH2Cl]0(M Rate

nt ) (M/s)

Initial

Experime [CH3CH2Cl]0(M Rate

nt ) (M/s)

Given: balanced chemical equation, initial concentrations of reactant, and initial rates of reaction

Strategy:

A. Compare the data from two experiments to determine the effect on the reaction rate of changing the concentrati

B. Compare the observed effect with behaviors characteristic of zeroth- and first-order reactions to determine the

the reaction.

C Use measured concentrations and rate data from any of the experiments to find the rate constant.

Solution:

The reaction order with respect to ethyl chloride is determined by examining the effect of changes in the ethyl chloride

A Comparing Experiments 2 and 3 shows that doubling the concentration doubles the reaction rate, so the reactio

Similarly, comparing Experiments 1 and 4 shows that quadrupling the concentration quadruples the reaction rate, aga

directly proportional to [CH3CH2Cl].

B This behavior is characteristic of a first-order reaction, for which the rate law is rate = k[CH3CH2Cl].

C We can calculate the rate constant (k) using any row in the table. Selecting Experiment 1 gives the following:

1.6 106 s1 = k

Exercise

Sulfuryl chloride (SO2Cl2) decomposes to SO2 and Cl2 by the following reaction:

Data for the reaction at 320C are listed in the following table. Calculate the reaction order with regard to sulfuryl chlo

for the reaction.

Exercise 1: I see you

Sulfuryl chloride (SO2Cl2) decomposes to SO2 and Cl2 by the following reaction:

Data for the reaction at 320C are listed in the following table. Calculate the reaction order with regard to sulfuryl chlo

for the reaction.

nt ) (M/s)

Figure 14.12 The Hydrolysis of Cisplatin, a First-Order Reaction. These plots show hydrolysis of cisplatin

at pH 7.0 and 25C as (a) the experimentally determined concentrations of cisplatin and chloride ions

versus time and (b) the natural logarithm of the cisplatin concentration versus time. The straight line in (b)

is expected for a first-order reaction.

We can also use the integrated rate law to determine the reaction rate for the hydrolysis of cisplatin. To do

this, we examine the change in the concentration of the reactant or the product as a function of time at a

single initial cisplatin concentration. Part (a) in Figure 14.12 shows plots for a solution that originally

contained 0.0100 M cisplatin and was maintained at pH 7 and 25C. The concentration of cisplatin

decreases smoothly with time, and the concentration of chloride ion increases in a similar way. When we

plot the natural logarithm of the concentration of cisplatin versus time, we obtain the plot shown in part (b)

in Figure 14.12. The straight line is consistent with the behavior of a system that obeys a first-order rate

law. We can use any two points on the line to calculate the slope of the line, which gives us the rate

constant for the reaction. Thus taking the points from part (a) in Figure 14.12 for t = 100 min ([cisplatin] =

0.0086 M) and t = 1000 min ([cisplatin] = 0.0022 M),

slopekk=ln[cisplatin]1000ln[cisplatin]1001000min100min=ln0.0022ln0.00861000min100min=6.12

(4.76)900min=1.51103min1=1.5103min1slope=ln[cisplatin]1000ln[cisplatin]1001000min100m

ink=ln0.0022ln0.00861000min100min=6.12

(4.76)900min=1.51103min1k=1.5103min1

The slope is negative because we are calculating the rate of disappearance of cisplatin. Also, the rate

constant has units of min1 because the times plotted on the horizontal axes in parts (a) and (b) in Figure

14.12 are in minutes rather than seconds.

The reaction order and the magnitude of the rate constant we obtain using the integrated rate law are

exactly the same as those we calculated earlier using the differential rate law. This must be true if the

experiments were carried out under the same conditions.

Example 5

Refer back to Example 4. If a sample of ethyl chloride with an initial concentration of 0.0200 M is heated at 650C

chloride after 10 h? How many hours at 650C must elapse for the concentration to decrease to 0.0050 M? (Recall tha

this reaction in Example 4.)

Asked for: concentration at specified time and time required to obtain particular concentration

Strategy:

A. Substitute values for the initial concentration ([A]0) and the calculated rate constant for the reaction (k) into th

reaction. Calculate the concentration ([A]) at the given time t.

B. Given a concentration [A], solve the integrated rate law for time t.

Solution:

The exponential form of the integrated rate law for a first-order reaction (Equation 14.20) is [A] = [A] 0ekt.

A Having been given the initial concentration of ethyl chloride ([A] 0) and having calculated the rate constant in Exam

the rate law to calculate the concentration of the reactant at a given time t. Substituting the known values into the inte

M(e(1.6106 s1)[(10 h)(60 min/h)(60 s/min)])=0.0189 M

We could also have used the logarithmic form of the integrated rate law (Equation 14.21):

s/min)]=3.9120.0576=3.970=e3.970 M=0.0189 Mln[CH3CH2Cl]10 h=ln[CH3CH2Cl]0kt=ln0.0200(1.61

s/min)]=3.9120.0576=3.970[CH3CH2Cl]10 h=e3.970 M=0.0189 M

B To calculate the amount of time required to reach a given concentration, we must solve the integrated rate law for t.

ln[CH3CH2Cl]tktt=ln[CH3CH2Cl]0kt=ln[CH3CH2Cl]0ln[CH3CH2Cl]t=ln[CH3CH2Cl]0[CH3CH2Cl]t=1k(ln[CH3CH2Cl]0[C

M0.0050 M)=ln4.01.6106 s1=8.7105 s=240 h=2.4102 hln[CH3CH2Cl]t=ln[CH3CH2Cl]0ktkt=ln[CH3CH2Cl]0ln[C

l]tt=1k(ln[CH3CH2Cl]0[CH3CH2Cl]t)=11.6106 s1(ln0.0200 M0.0050 M)=ln4.01.6106 s1=8.71

Exercise 5

In the exercise in Example 4, you found that the decomposition of sulfuryl chloride (SO 2Cl2) is first order, and you calcu

the form(s) of the integrated rate law to find the amount of SO 2Cl2 that remains after 20 h if a sample with an original

320C. How long would it take for 90% of the SO2Cl2 to decompose?

Answer: 0.0252 M; 29 h

We will illustrate the use of these graphs by considering the thermal decomposition of NO 2 gas at elevated

temperatures, which occurs according to the following reaction:

(2NO2(g)2NO(g)+O2(g)(1.1)(1.1)(2NO2(g)2NO(g)+O2(g)

Experimental data for this reaction at 330C are listed in Table 14.5; they are provided as [NO2], ln[NO2],

and 1/[NO2] versus time to correspond to the integrated rate laws for zeroth-, first-, and second-order

reactions, respectively. The actual concentrations of NO 2 are plotted versus time in part (a) in Figure 14.15.

Because the plot of [NO2] versus t is not a straight line, we know the reaction is not zeroth order in NO 2. A

plot of ln[NO2] versus t (part (b) in Figure 14.15) shows us that the reaction is not first order in NO 2 because

a first-order reaction would give a straight line. Having eliminated zeroth-order and first-order behavior, we

construct a plot of 1/[NO2] versus t (part (c) in Figure 14.15). This plot is a straight line, indicating that the

reaction is second order in NO2.

NO2 as a Function of Time at

330C

Ti [NO2 ln[ 1/

m ] (M) NO2 [NO

e ] 2]

(s (M1

) )

102 05

103 86

0 103 63

Table 14.5: Concentration of

NO2 as a Function of Time at

330C

Ti [NO2 ln[ 1/

m ] (M) NO2 [NO

e ] 2]

(s (M1

) )

0 103 77

0 103 55

0 103 06

0 103 37

Figure 1.11.1: The Decomposition of NO2. These plots show the decomposition of a sample of NO2 at

330C as (a) the concentration of NO2 versus t, (b) the natural logarithm of [NO2] versus t, and (c) 1/[NO2]

versus t.

We have just determined the reaction order using data from a single experiment by plotting the

concentration of the reactant as a function of time. Because of the characteristic shapes of the lines shown

in Figure 1.21.2, the graphs can be used to determine the reaction order of an unknown reaction. In

contrast, the method of initial rates required multiple experiments at different NO 2 concentrations as well

as accurate initial rates of reaction, which can be difficult to obtain for rapid reactions.

Figure 1.21.2: Properties of Reactions That Obey Zeroth-, First-, and Second-Order Rate Laws

Example 1.11.1

Dinitrogen pentoxide (N2O5) decomposes to NO2 and O2 at relatively low temperatures in the following

reaction:

This reaction is carried out in a CCl 4 solution at 45C. The concentrations of N 2O5 as a function of time are

listed in the following table, together with the natural logarithms and reciprocal N 2O5 concentrations. Plot a

graph of the concentration versus t, ln concentration versus t, and 1/concentration versus t and then

determine the rate law and calculate the rate constant.

e (M) 5] [N2O5]

(s) (M1)

5

4

0 6

180 0.015 4.154 63.7

0 7

0 7

0 60

0 40

Strategy:

A Use the data in the table to separately plot concentration, the natural logarithm of the concentration,

and the reciprocal of the concentration (the vertical axis) versus time (the horizontal axis). Compare the

graphs with those in Figure 14.16 to determine the reaction order.

B Write the rate law for the reaction. Using the appropriate data from the table and the linear graph

corresponding to the rate law for the reaction, calculate the slope of the plotted line to obtain the rate

constant for the reaction.

SOLUTION

A Here are plots of [N2O5] versus t, ln[N2O5] versus t, and 1/[N2O5] versus t:

The plot of ln[N2O5] versus t gives a straight line, whereas the plots of [N 2O5] versus t and 1/[N2O5]

versus t do not. This means that the decomposition of N2O5 is first order in [N2O5].

rate = k[N2O5]

Calculating the rate constant is straightforward because we know that the slope of the plot of ln[A]

versus t for a first-order reaction is k. We can calculate the slope using any two points that lie on the line

in the plot of ln[N2O5] versus t. Using the points for t = 0 and 3000 s,

(1.2)slope=ln[N2O5]3000ln[N2O5]03000 s0 s=(4.756)(3.310)3000 s=4.820104 s1

Exercise 1.11.1

1,3-Butadiene (CH2=CHCH=CH2; C4H6) is a volatile and reactive organic molecule used in the production

of rubber. Above room temperature, it reacts slowly to form products. Concentrations of C 4H6 as a function

of time at 326C are listed in the following table along with ln[C 4H6] and the reciprocal concentrations.

Graph the data as concentration versus t, ln concentration versus t, and 1/concentration versus t. Then

determine the reaction order in C4H6, the rate law, and the rate constant for the reaction.

Ti [C4H6] ln[C4 1/

me (M) H6] [C4H6]

(s) (M1)

02 3

02 7

0 02 8

0 03 4

600 7.30 1 4.92 137

0 03 0

Answer:

Summary

For a zeroth-order reaction, a plot of the concentration of any reactant versus time is a straight line with a

slope of k. For a first-order reaction, a plot of the natural logarithm of the concentration of a reactant

versus time is a straight line with a slope of k. For a second-order reaction, a plot of the inverse of the

concentration of a reactant versus time is a straight line with a slope of k.

Key Takeaway

Problem 2: The inversion of sucrose according to the reaction C 12H22O11 + H2O ---> 2C6H12O6, was observed at

25C and the experimental times and concentrations are given below. The initial concentration of sucrose was 1.0023

moles per liter.

Using the graph below, verify the reaction is first order, and calculate the rate constant.

Problem 3: The decomposition reaction SO2Cl2(g) ---> SO2(g) + Cl2(g) is a first order reaction with rate constant k=2.2

x 10-5 sec-1 at 320C. What percent of SO2Cl2 is decomposed at 320C after 90 minutes?

Problem 4: Fales and Morrell [J. Am. Chem. Soc. 44, 2071 (1922)] measured the inversion of

sucrose in the presence of hydrochloric acid. Their approach was to measure the angle of

rotation of polarized light passed through the sucrose solution. They obtained the following

data. Plot the logarithm of (t)-(inf))/(0)-(inf)) versus t to find the rate constant of this first

order reaction.

0 11.20

1035 10.35

3113 8.87

4857 7.64

9231 5.19

12834 3.61

18520 1.60

26320 -0.16

32640 -1.10

76969 -3.26

inf -3.37

Glossary of Terms

Stoichiometry determines the molar ratios of reactants and products in an overall chemical reaction. We express

the stoichiometry as a balanced chemical equation. For kinetics it is convient to write this as products minus

reactants: npP + nqQ - naA - nbB (instead of the conventional equation n aA + nbB ---> npP + nqQ). This indicates that

na and nb moles of reactants A and B, resp., produce n p and nq moles of products P and Q.

The rate of a chemical reaction is defined in such a way that it is independent of which reactant or product is

monitored. We define the rate, v, of a reaction to be v = (1/n g) d[G]/dt where ng is the signed (positive for products,

negative for reactants) stoichiometric coefficient of species G in the reaction. Namely, v = (-1/n a) d[A]/dt = (1/np)

d[P]/dt, etc.

It is convenient to refer to the extent of reaction. As the reactants are sonsumed and the products are produced,

their concentrations change. If the initial concentrations of A, B, P and Q are [A], [B], [P] and [Q], resp., then the

extent of reaction is defined: = -([A]-[A]0)/na = -([B] - [B]0)/nb = ([P]-[P]0)/np = ([Q]-[Q]0)/nq. Alternately, each species

concentration is a function of the extent of reaction: [A] = [A] 0 - na, etc.

Many reactions follow elementary differential rate laws such as v = k f([A], [B], ...) where f([A], [B], ...) is a

function of the concentrations of reactants and products. That is, the rate varies as the concentrations change. A

proportionality constant, k, is called the rate constant of the reaction.

When the rate law has the special form of a product (or quotient) of powers, f([A], [B], ...) =

[A]a [B]b [P]p [Q]q then a is the order of the reaction with respect to A, b is the order w.r.t. B, etc. Note that order may

be positive, negative, integer, or non-integer. Further, the sum a + b + p + q is the overall order of the reaction rate

law.

NOTE: there is no necessary relation between orders and stoichiometric coefficients. That is, a might differ from

na.

Reaction rate constants are usually temperature dependent; the rate of a reaction usually increases as the

temperature rises. The temperature dependence often follows Arrhenius' equation: k(T) = A exp(-Ea/RT) where T is

the absolute temperature, R the universal gas constant, Ea is the activation energy (specific to each reaction), and A

is the "pre-exponential" or "frequency" or "entropy" factor.

One objective of chemical kinetics is to solve the differential rate law d[G]/dt = k f([A], [B], ...), and thereby

express each species concentration as a function of time: [G](t). Since solution requires integration, we call it the

integrated rate law.

A reaction mechanism is a set of steps at the molecular level. Each step involves combinations or re-

arrangements of individual molecular species. The steps in combination describe the path or route that reactant

molecules follow to reach the product molecules. The result of all steps is to produce the overall balanced

stoichiometric chemical equation for reactants producing products.

The following graphs represents concentration of reactants versus time for a first-order reaction.

Plotting ln[A]ln[A] with respect to time for a first-order reaction gives a straight line with the slope of the

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